JP2004277382A - Composition for eliminating pollution element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pollution component eliminating agent effective for efficiently decomposing various polluting elements and having good usability. <P>SOLUTION: A composition containing an extract obtained by extracting a sedimentary rock soil containing basalt and/or andesite with an acid as an active component is used as the polluting component eliminating agent. The composition develops deodorizing and bactericidal action based on the oxidation reduction reaction of an inorganic component of the extracted liquid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

表１に示すように、いずれも５分間の暴露で顕著な成分の消去活性を確認することができた。
【００２６】
（実施例３）
実施例１で調製した抽出液を滅菌精製水で１００倍希釈した希釈液を試験液として、メチシリン耐性黄色ブドウ球菌（ＭＲＳＡ）の菌液と添加し混合し、２５℃で５分、１０分、３０分間作用後に生菌数を測定した。なお、詳細な試験条件は以下の通りとした。
１．試験菌
Ｓｔａｐｈｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＩＩＤ １６７７（ＭＲＳＡ）
２．試験用培地
ＮＡ培地：普通寒天培地（栄研化学株式会社製）
ＳＣＤＬＰ培地：ＳＣＤＬＰ培地（日本製薬株式会社）
ＳＣＤＬＰＡ培地：ＳＣＤＬＰ寒天培地（日本製薬株式会社）
３．菌液の調製
試験菌をＮＡ培地で３５℃±１℃、１６〜２０時間培養した。培養後の菌体を滅菌生理食塩液水に１ｍｌ当たりの菌数が約１０^７となるように浮遊させ菌液とした。
４．試験操作
滅菌精製水を用いて検体の１００倍希釈液を調製し、試験液とした。試験液５０ｍｌに菌液０．５ｍｌをそれぞれ添加し、混合し、２５℃±１℃で５分、１０分及び１５分作用後に、ＳＣＤＬＰ培地を用いて直ちに１０倍に希釈した。この希釈液の生菌数を、ＳＣＤＬＰＡ培地を用いた混釈平板培養法（３５℃±１℃、２日間培養）により測定し、試験液１ｍｌ当たりに換算した。
なお、予め予備試験を行い、生菌数の測定方法について検討した。
結果を表２に示す。
【００２７】
【表２】

表２に示すように、３０分経過後において、菌数が１０００分の１以下に減少しており、顕著なＭＲＳＡの除菌作用を確認することができた。
【００２８】
【発明の効果】
本発明によれば、各種の汚染要素を効率的に分解する使用性のよい汚染成分消去剤を提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a composition for eliminating organic or inorganic contaminants using an acidic extract from soil as an active ingredient, and more particularly to a composition effective for sterilization and deodorization.
[0002]
[Prior art]
In recent years, the presence of organic contaminants in the environment has become a major problem, and at the same time, research and development of removing agents and devices for decomposing or removing these substances have been actively conducted.
Although various studies have been made, most of the methods are based on decomposition of pollutants by a photocatalyst, decomposition by strong oxidizing power using a radical generating compound such as hydrogen peroxide, or adsorption of contaminants (Patent Document 1). ).
[0003]
[Patent Document 1]
JP-A-2002-361095
[0004]
[Problems to be solved by the invention]
However, in the case of a compound that decomposes pollutants, it has a strong oxidizing power itself, so that it cannot be sprayed anywhere or anytime, and in the case of a photocatalyst, the form in which it acts is limited. There were things.
An object of the present invention is to provide a contaminant eliminator that decomposes various contaminants efficiently and with good usability.
[0005]
[Means for Solving the Problems]
The present inventors have found that an extract obtained by acid-extracting sedimentary rock soil under certain conditions has deodorizing and disinfecting effects, and completed the present invention.
That is, according to the present invention, the following means are provided.
(1) An extract obtained by acid-extracting sedimentary rock soil containing basalt and / or andesite, and a stock solution for eliminating contaminants, containing sodium chloride and / or an organic acid.
(2) The stock solution according to (1), wherein the composition contains iron as a main component as a metal component and contains silicon, manganese, titanium, magnesium, and calcium.
(3) ^Fe 3+ at pH3 or less, pH3 super 4 and ^{Fe 3+} and Fe ^{(OH) 2+} in the following, the ^{Fe 3+} and Fe ^{(OH) 2+} and Fe _(OH) ^{2 +} and is 5 or less in pH4 greater, pH 5 and the ultra-preparative Fe ^{(OH) 2+} and Fe _(OH) ^{2 +} and Fe _{(OH) 3} as a main present embodiment, the stock solution according to (1) or (2).
(4) The stock solution according to any one of (1) to (3), wherein the stock solution has an iron content of 13000 ppm or more.
(5) The stock solution according to any one of (1) to (4), wherein the sum of the amount of magnesium and the amount of calcium with respect to the iron content in the stock solution is less than 30 wt%.
(6) The stock solution according to (1) to (5), wherein the extract is a supernatant obtained by adding water and an organic acid to the sedimentary rock soil, then adding an inorganic acid, and heating.
(7) A composition for removing contaminants obtained by diluting the stock solution according to any one of (1) to (6) with water and / or an organic solvent.
(8) A composition for eliminating contaminants, comprising an extract obtained by acid-extracting sedimentary rock soil containing basalt and / or andesite, and sodium chloride and / or citric acid.
(9) The composition according to (7) or (8), wherein the composition has a pH of 2.0 or more and an iron content of 10 ppm or more.
(10) A method for producing a stock solution for removing contaminant components,
Mixing the sedimentary rock soil containing basalt and / or andesite with water and an organic acid,
A step of adding an inorganic acid to the mixed solution and heating,
Collecting the supernatant liquid after the heating,
A method comprising:
(11) The method according to (10), further comprising a step of adding sodium chloride and / or an organic acid to the supernatant.
(12) A method for producing a stock solution for removing contaminant components,
Heating the sedimentary rock soil containing basalt and / or andesite by adding water and an inorganic acid and mixing;
Collecting the supernatant liquid after the heating,
A step of adding sodium chloride and / or an organic acid to the supernatant,
A method comprising:
(13) A stock solution for removing contaminants obtained by the method according to any one of (10) to (12).
[0006]
ADVANTAGE OF THE INVENTION According to this invention, the contaminant removal composition which is a natural origin, has high contaminant removal performance, and the restriction | limiting about the application place was reduced is provided.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
The contaminant-removing composition of the present invention contains, as an active ingredient, an extract obtained by acid-extracting sedimentary rock soil containing basalt and / or andesite. In addition, the undiluted solution for removing contaminant components contains the extract as a main component. Hereinafter, the extract and its manufacturing method will be described, and then its contaminant removing action will be described.
In the present invention, the term "contaminant component" includes pests (especially microorganisms) in addition to compounds that are harmful to the environment and / or humans, regardless of whether they are organic or inorganic.
[0008]
The extract in the present invention is an extract obtained by acid-extracting sedimentary rock soil containing andesite and / or basalt (preferably including both andesite and basalt). It is preferable that the sedimentary rock soil belongs to the order of Ultisol in terms of taxonomic classification. The soil belonging to the order is generally collected as tropical red-yellow soil. The soil of this eye is characterized by low organic matter content, high clay content, and the main clay mineral is kaolinite with low surface charge. Therefore, soil pH often exhibits acidity. Preferably, it is a sedimentary rock soil containing both andesite and basalt.
[0009]
The method of extraction from soil is to extract the acid-soluble component by acid extraction, but preferably the following mode can be adopted.
As the acid, one or more selected from inorganic acids and organic acids can be used. As the inorganic acid, various inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like can be used, but preferably, sulfuric acid is used. A preferable extraction efficiency can be obtained in the range of about 10 wt% or more and about 20 wt% or less as the sulfuric acid concentration. Sulfuric acid can be used alone, but in that case it is preferably about 20 wt%.
As the organic acid, an organic acid having one or two or more carboxyl groups can be used. That is, formic acid, acetic acid, ascorbic acid, citric acid and the like can be used. Preferably, citric acid and / or ascorbic acid can be used as the organic acid. This is because the use of ascorbic acid or citric acid can increase the recovery of iron in the soluble component. As the organic acid, it is preferable to use the organic acid at a concentration of about 3 wt% or less and about 10 wt% or less in the extraction system. In particular, it is preferable that the concentration of citric acid be 0.1 M or more and 0.5 M or less. If it is less than 0.1 M, it is difficult to obtain a sufficient chelating effect, and if it exceeds 0.5 M, it is difficult to generate ferrihydrite.
The organic acid is preferably used in combination with an inorganic acid such as sulfuric acid. When used in combination with an inorganic acid, it is preferable that the inorganic acid in the extraction system is 10 wt% to 18 wt% and the organic acid is 3 wt% to 10 wt%. Further, it is preferable that the weight ratio of the organic acid to the inorganic acid is 30 wt% or less and 60 wt% or less.
[0010]
The acid is supplied to soil suspended in water. When an organic acid and an inorganic acid are used in combination, it is preferable that a predetermined amount of the organic acid is previously added to and mixed with the soil suspension, and then the inorganic acid is added.
A predetermined amount of acid is added, and the mixture is heated simultaneously or successively to a predetermined temperature to extract an acid-soluble component in soil. The extraction temperature is preferably, for example, 70 ° C. or higher and lower than 100 ° C. If the temperature is lower than 70 ° C., it tends to be difficult to remove iron ions from the clay fraction. If the temperature is higher than 100 ° C., evaporation of water and energy costs are likely to occur, and furthermore, the extraction apparatus is likely to be deteriorated. . More preferably, the temperature is about 80 ° C. The extraction time can be in the range of 1 hour to 120 hours, and is usually 80 hours or more and 100 hours or less.
[0011]
After heating for a predetermined time, the supernatant containing the acid-soluble component can be collected by filtration through a filter or the like.
This supernatant is the extract in the present invention. The present extract typically has the following properties.
This extract contains iron as a main component as a metal, and also contains silicon, manganese, titanium, magnesium and calcium in addition to iron. Here, the total amount of the magnesium content and the calcium content in the extract is less than 30 wt% of the iron content, preferably less than 20 wt%, and more preferably less than 15 wt%.
Further, the iron content is preferably 7000 ppm or more. If the iron content is less than the above amount, the effect of the acid used at the time of extraction becomes strong, and the effect of the inorganic component of the present extract is hardly exhibited. More preferably, it is not less than 10,000 ppm and not more than 20,000 ppm. Most preferably, it is 13000 ppm or more and 16000 ppm or less. Iron content can be measured by o-phenanthroline absorption spectrophotometry, and calcium and magnesium can be measured by atomic absorption spectrophotometry.
Further, sodium is preferably 0.3 wt% or more and 0.5 wt% or less with respect to iron content, potassium is preferably 0.7 wt% or more and 1.0 wt% or less, and manganese is 1.0 wt% or less. It is preferably at least 1.5 wt%.
Similarly, the content of titanium is preferably 0.1 wt% or more and 0.5 wt% or less.
[0012]
The pH of the present extract is about 0.1 to 0.2, and the sulfate ion content is about 10 wt% or more and about 20 wt% or less, depending on the amount used during acid extraction. Further, when an organic acid such as ascorbic acid is used at the time of extraction, the organic acid is also included. For example, the organic acid content is about 3 wt% or more and about 10 wt% or less.
[0013]
Further, in the present extract, iron exists in different forms as the pH changes. That, ^Fe 3+ at pH3 or less, pH3 super 4 and ^{Fe 3+} and Fe ^{(OH) 2+} in the following, the ^{Fe 3+} and Fe ^{(OH) 2+} and Fe _(OH) ^{2 +} and is 5 or less in pH4 greater, pH 5 than In this example, Fe (OH) ²⁺ , Fe (OH) ₂ ^+, and Fe (OH) ₃ are mainly present.
[0014]
That is, this extract contains Fe ³⁺ that can generate a secondary oxide such as ferrihydrite (Ferrihydrite; general formula 5FeO ₃ .9H ₂ O: amorphous iron hydrated oxide). However, it is presumed that the Fe ³⁺ changes to Fe ²⁺ when producing ferrihydrite, thereby oxidizing other substances and exhibiting various pollutant decomposing effects.
Ferrihydrite is known to have the property of coordinating with the OH end of the carboxyl group or carbonyl group of an organic compound and to form an aggregate. Further, it has a specific surface area of about 200 m ² / g, and has a wide field for reaction with contaminant components such as organic compounds. Therefore, it is presumed that the ability to capture, fix, remove and decompose contaminant components is high.
The extract contains a polymer-like compound derived from a clay mineral and produced or extracted by acid extraction, and the diameter of the polymer is about 3 nm to 5 nm.
[0015]
On the other hand, the extraction residue contains pure iron (Fe ²⁺ ) and amorphous goethite (α-FeOOH). Further the measured residue with Mossbauer spectroscopy, paramagnetic ^{Fe 2+} and spinel octahedral positions of the _Fe 3 _{O 4,} and _Fe 3 _{O 4} of spinel tetrahedral position, the _α-Fe 2 _{O 3} contains I knew I was out. By analyzing such a residue, it is also possible to specify the extraction step of the extract in the present invention.
[0016]
Further, sodium chloride and / or an organic acid such as a natural salt can be separately added to the present extract. Sodium chloride may be added alone, but it is preferable to add sodium chloride as a main component and other metal salts such as sodium metal. More preferably, it is added as an unpurified salt (a so-called natural salt). Further, as the salt containing sodium chloride as a main component, a so-called roasted salt baked at 250 ° C. or higher can be used. More preferably, it is a baked salt of a natural salt.
The addition of the salt can enhance the action of removing contaminants. The amount of salt added is preferably 5 wt% or more and 20 wt% or less in the extract.
The organic acid is preferably various carboxylic acids, and typically citric acid or ascorbic acid can be added. Preferably citric acid. By adding an organic acid, the action can be exerted continuously.
The carboxylic acid may be a salt such as sodium or a free acid. The amount of addition is preferably 5 wt% or more and 40 wt% or less in the extract. When the organic acid is also used in the extraction step, it is preferable to newly add 1.0 to 5.0 wt% of the extract to the extract.
[0017]
Such an extract has a high activity of decomposing and removing organic and inorganic pollutants, but is effective in a small amount. Therefore, the present extract or a liquid obtained by adding a salt and / or an organic acid thereto is provided as it is as a stock solution, and is appropriately diluted with tap water or the like as appropriate, and used as a contaminant removing agent that can be widely and safely applied. be able to.
As the diluting liquid, in addition to water such as tap water, alcohol such as ethanol can be used. Alternatively, a mixed solution of water and alcohol can be used.
The dilution liquid can be selected according to the application site and the like.
[0018]
The dilution ratio can be set as appropriate depending on the application and the concentration of the contaminant. However, garbage collection sites, disposal sites, incineration plants, garbage pits, packers, livestock pens, compost factories, compost material collection sites, human waste treatment plants, and recycling Disposal site, PET bottle disposal site, Bottle sorting machine, Commercial composting machine, Weight reduction garbage disposal machine, Composting plant, Automobile demolition plant, Used car recycling plant, Sewage, Sludge, Gas, Sewage sludge, Food processing When used in places, fishing grounds, fish processing plants, pools, baths, saunas, nursing homes, hospitals, commercial kitchens, animal breeding areas, homes, etc., deodorize by diluting 100-fold to 5000-fold. And eradication is possible. Preferably, it is 1000 times to 5000 times. Most preferably, it is 1200 to 3000 times.
[0019]
Therefore, by diluting the stock solution as appropriate, spraying, applying, or the like, and applying it to a site where a contaminant component exists or a site where such a contaminant may exist, it is possible to effectively exert a contaminant component removing effect. .
[0020]
Further, the stock solution can be provided as the present composition in a state of being diluted in advance. The present contaminant removing composition contains the stock solution as an active ingredient. The stock solution is essentially acidic, and the composition preferably has a pH of 2.0 or more, more preferably 4.0 or more, and more preferably 5 or more, from the viewpoint of ensuring safety during application. 0.0 or more, and most preferably neutral pH 6.0 or more and 8.0 or less.
The iron content is preferably 5 ppm or more, more preferably 10 ppm or more. The upper limit is not particularly limited, but can be 50 ppm or less. Most preferably, it is 10 ppm or more and 20 ppm or less.
When this stock solution is diluted 100 times with tap water as dilution water, the pH of the 100-fold diluted solution is about 2.5, the pH of the 3000-fold diluted solution is slightly less than 5, and the pH of the 5000-fold diluted solution is The pH of the 7,000-fold diluted solution is about 6.0 to 6.5, and the pH of the 10,000-fold diluted solution is about 7, about 5.5 to 6.0.
[0021]
As described above, the present stock solution and the present composition can decompose and remove organic and inorganic contaminants by the oxidizing power of the precursor, which produces ferrihydrite contained in the extract, and as a result, deodorization and sterilization can be performed. I do. This oxidizing power is due to the change from Fe ³⁺ to Fe ²⁺ , while returning this Fe ²⁺ back to Fe ³⁺ enables the deodorizing and sterilizing effects to be exerted continuously. That is, according to the present invention, it is safe to use a redox reaction based on a natural inorganic component as a main component without using a conventional deodorant and sterilization by a compound that generates a strong oxidizing power. In addition, a highly effective deodorant and disinfectant can be provided.
[0022]
【Example】
Hereinafter, specific examples of the present invention will be described with reference to examples, but the present invention is not limited to the following examples. The present invention can be implemented in various modes within the scope of the present invention.
[0023]
(Example 1)
Preparation of Extract A water suspension was prepared by adding and mixing 2370 g of water to 1775 g of red loess collected in the tropics, which is an Artisol soil. After adding and mixing 265 g of ascorbic acid to this suspension, 590 g of sulfuric acid (concentrated sulfuric acid) was added, and the mixture was heated to about 80 ° C. and extracted for 4 days. The extract was filtered to collect 1.2 L of an extract containing an acid-soluble component. The iron content in this extract was measured by o-phenanthroline absorptiometry and was found to be 1.50 wt% (15000 ppm). The manganese content measured by atomic absorption spectrometry was 189 ppm.
[0024]
(Example 2)
Evaluation of deodorant ability The extract prepared in Example 1 was subjected to an ammonia and trimethylamine deodorant test using various diluents diluted with purified water and 89% ethanol. Table 1 shows the mode of dilution with each diluent and the results of the deodorizing test.
The test was conducted by introducing a gas of about 100 ppm of ammonia or about 20 ppm of trimethylamine into a 1-liter Tedlar bag, then adding 5 ml of a sample solution to the Tedlar bag, sealing, and shaking for 1 minute. The gas concentration was measured 5 minutes and 10 minutes after the addition of the sample liquid. In addition, the detection method of the residual gas concentration was based on the detection tube method. Ammonia is Kitagawa No. 105SC and SD were used, and gastech 180 and 180 L were used as trimethylamine.
[0025]
[Table 1]

As shown in Table 1, remarkable erasure activity of the components was confirmed in each case after exposure for 5 minutes.
[0026]
(Example 3)
A diluted solution obtained by diluting the extract prepared in Example 1 100 times with sterile purified water was used as a test solution, added to and mixed with a methicillin-resistant Staphylococcus aureus (MRSA) bacterial solution, and mixed at 25 ° C. for 5 minutes and 10 minutes. After 30 minutes of action, the viable cell count was determined. The detailed test conditions were as follows.
1. Test bacteria Staphlococcus aureus IID 1677 (MRSA)
2. Test medium NA medium: Normal agar medium (manufactured by Eiken Chemical Co., Ltd.)
SCDLP medium: SCDLP medium (Nippon Pharmaceutical Co., Ltd.)
SCDLPA medium: SCDLP agar medium (Nippon Pharmaceutical Co., Ltd.)
3. Preparation of bacterial solution The test bacteria were cultured in an NA medium at 35 ° C ± 1 ° C for 16 to 20 hours. The cultured cells were suspended in a sterilized physiological saline solution so that the number of cells per 1 ml was about 10 ⁷ to obtain a bacterial solution.
4. Test operation A 100-fold diluted solution of the specimen was prepared using sterile purified water, and used as a test solution. 0.5 ml of the bacterial solution was added to 50 ml of the test solution, mixed, and after 5 minutes, 10 minutes and 15 minutes of action at 25 ° C. ± 1 ° C., the mixture was immediately diluted 10-fold with an SCDLP medium. The viable cell count of this diluted solution was measured by a pour plate culture method (cultured at 35 ° C. ± 1 ° C. for 2 days) using an SCDLPA medium, and was converted per 1 ml of the test solution.
In addition, a preliminary test was performed in advance, and the measurement method of the viable cell count was examined.
Table 2 shows the results.
[0027]
[Table 2]

As shown in Table 2, after 30 minutes, the number of bacteria was reduced to 1/1000 or less, and a remarkable MRSA eradication effect was confirmed.
[0028]
【The invention's effect】
Advantageous Effects of Invention According to the present invention, it is possible to provide an easily usable contaminant eliminator that efficiently decomposes various contaminants.

Claims (13)

An undiluted solution for elimination of polluting components, comprising an extract obtained by acid-extracting sedimentary rock soil containing basalt and / or andesite, and sodium chloride and / or an organic acid. The stock solution according to claim 1, wherein the composition contains iron as a main component as a metal component and contains silicon, manganese, titanium, magnesium, and calcium. When the pH is 3 or less, Fe ³⁺ , when the pH is more than 3 and 4, Fe ³⁺ and Fe (OH) ²⁺ , when the pH is more than 4 the Fe ³⁺ and Fe (OH) ²⁺ and Fe (OH) ₂ ⁺ are used. Fe ^{(OH) 2+} and Fe _(OH) and ^{2 +} and Fe _{(OH) 3} as a main present embodiment, the stock solution according to claim 1 or 2. The stock solution according to any one of claims 1 to 3, wherein the stock solution has an iron content of 13000 ppm or more. The stock solution according to any one of claims 1 to 4, wherein the sum of the amount of magnesium and the amount of calcium with respect to the iron content in the stock solution is less than 30 wt%. The stock solution according to any one of claims 1 to 5, wherein the extract is a supernatant obtained by adding water and an organic acid to the sedimentary rock soil, then adding an inorganic acid, and heating. A contaminant removing composition obtained by diluting the stock solution according to any one of claims 1 to 6 with water and / or an organic solvent. A composition for eliminating contaminants, comprising an extract obtained by acid-extracting sedimentary rock soil containing basalt and / or andesite, and sodium chloride and / or citric acid. The composition according to claim 7, wherein the composition has a pH of 2.0 or more and an iron content of 10 ppm or more. A method for producing a stock solution for removing contaminant components,
Mixing the sedimentary rock soil containing basalt and / or andesite with water and an organic acid,
A step of adding an inorganic acid to the mixed solution and heating,
Collecting the supernatant liquid after the heating,
A method comprising: The method according to claim 10, further comprising a step of adding sodium chloride and / or an organic acid to the supernatant. A method for producing a stock solution for removing contaminant components,
Heating the sedimentary rock soil containing basalt and / or andesite by adding water and an inorganic acid and mixing;
Collecting the supernatant liquid after the heating,
A step of adding sodium chloride and / or an organic acid to the supernatant,
A method comprising: A stock solution for removing contaminant components obtained by the method according to claim 10.